Amino-anthraquinone compounds containing a trifluoromethyl group and a polyfluoroalkylamino group



Patented Jan. 16, 1951 UNITED STATES WiTENT OFFICE AMINO-ANTHRAQUINONECDMPOUNDS CONTAINING A TRIFLUUROMETHYL GROUP AND A POLYFLUOROALKYL-AMEND GROUP Joseph B. Dickey and Edmund B. Towne, Rochester, N. Yassignors to Eastman Kodak Company, Rochester, N. K,

.llersey a corporation of New No Drawing. Application October 6, 1948,

Serial No.

4 Claims.

C CF: 1

a i i-Ry H wherein R stands for a member selected from the groupconsisting of a hydrogen atom, an alkyl group having 1 to 4 carbonatoms, a hy-- droxyalkyl group having 2 to 3 carbon atoms, aCH,CH2OCH2CH2OH group and a -CHzCH2-O-CH2CH2--O-CH2CH2OH group and Rstands for a member selected from the group consisting of a2,2-difiuoroethyl group, a 2,2-difluoropropyl group, a3,3-difluoropropyl group, a 3,3-difluorobutyl group, a2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, anatrifluoromethylethyl group and an w-dlflUOl'O- methylethyl group arevaluable dyes for coloring textile materials made of or containing acel- .lulose alkyl carboxylic acid ester having two to four carbon atomsin the acid groups thereof. They are particularly of use for thecoloration of cellulose acetate textile materials.

It is an object of our invention to provide new anthraquinone dyecompounds. Another object is to provide a satisfactory process for thepreparation of the new anthraquinone dye compounds of the invention. Afurther object is to provide dyed cellulose alkyl carboxylic acid estertextile materials which possess good to ex- 40 cellent fastness to lightand gas. A particular object to provide new anthraquinone compoundswhich are especially of value for the dyeing of cellulose acetatetextile materials.

By cellulose alkyl carboxylic acid esters havlog two to four carbonatoms in the acid groups thereof we mean to include, for example, bothhydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate,cellulose butyrate, cellulose acetatapropionate and cellulose acetate-bu5O tyrate. Our new anthraouinone compounds color textile materials madeof the aforesaid cellulose allayl carboxylic acid esters blue, red blueviolet shades.

The anthraquinone compounds of our invention are prepared by condensingan anthraquinone compound having the formula:

wherein R has the meaning previously assigned to it with a primary aminehaving the formula:

wherein R1 has the meaning previously assigned to it. The condensationis ordinarily efiected under reflux in the presence of an inert diluentsuch as normal butyl alcohol, normal amyl alcohol or pyridine. Normallythe condensation reaction just referred to is carried out in thepresence of a copper salt catalyst although in some instances thepresence of a catalyst is not necessary. So far as we are aware almostany cupric salt is useful as a catalyst. Thus, cupric sulfate (eitherwith or without Water of crystallization), cupric acetate, cupricbromide, cupric chloride and cupric iodide can be used. lhe use ofcupric sulfate and cupric acetate is preferred. Similarly, anacid-binding agent such as potassium acetate is usually present duringthe reaction.

As indicated in the examples, the compounds can he purified bycrystallization from a solvent such as xylene or toluene. Also, whilethe utility of the compounds of our invention will be illustrated withreference to the dyeing or coloration of cellulose acetate textilematerials, it will be understood that they color the other textilematerials referred to hereinbefore generally similar shades.

The following examples illustrate the anthraquinone compounds of ourinvention and the manner in which they may be prepared.

Example 1 10 grams of lamino-2-trifluoromethyl-4- bromoanthraquinone areheated under reflux in cc. of normal butyl alcohol with 5 grams of2,2,2-trifluoroethylamine using 0.1 gram of copper sulfate as a catalystand 3 grams of potassium acetate to react with the hydrogen bromide thatforms. When no further color change toward the violet (3-6 hours) occursthe reaction is stopped, the reaction mixture is filtered while hot. anthe filtrate. obtained is con ent at d to 50 cc. by distillation underreduced pressure and cooled in a refrigerator. Upon filtration, acrystalline dye compound having the formula:

is obtained. If desired, it may be purified by crystallization fromxylene or toluene. It colors cellulose acetate textile materials violetshades from an aqueous suspension.

Example 2 g iii-camera crystallizes out and is recovered by filtration.Ii desired, it may be purified by crystallization from xylene ortoluene. It colors cellulose acetate textile materials reddish-blueshades from an aqueous suspension.

Example 3 10 grams of 1-B-hydroxyethylamino-2-triiiuoromethyll-bromoanthranthraquinone, 3 grams of potassium acetate, 4 grams of2,2,2-trifiuoroet-hy'larnine, 0.1 gram of copper sulfate and 196 cc. ofn-butyl alcohol are heated under reflux until no furthercolor changetakes place. ihe reaction mixture is filtered While hot and the filtrateis concentrated by distillation under reduced pressure to about l cc.Upon cooling, l-fi-hydroxyethylamino 2 trifiuoromethyl-l-trifiuoroethylamino-anthraquinone precipitates out and 'is recovered byfiltration. It has the formula:

and colors cellulose acetate textile materials reddish-blue shades froman aqueous suspension.

Example 4 10 grams ofl-methylamino-2-trifiuoromethyla-bromoanthraquinone, 5 grams of 2,2Z-trifluoroethylamine, 180 cc. of n-butyl alcohol, 3 grams of potassiumacetate and. 3.1 gram of copper sul- 4 l fate are refluxed togetheruntil no further color shift toward reddish-clue takes place. Thereaction mixture is filtered hot, concentrated to 35 cc. and cooled.1-methylamino-2-trifiuoromethyl i-trifluoroethylamino-anthraquinoneprecipitates out and is recovered by filtration. It colors celluloseacetate textile materials red-blue shades from an aqueous suspension.

Example 5 16 grams of 1amino2'trifiuoromethyl-4- bremcanthraquinone, 5grams of 1,1,l-trifluor0- 2-aminopropane 3 grams of potassium acetate,0.1 gram of copper sulfate and 3.00 cc. of n butyl alcohol are heatedtogether under refluxing conditions until no further color change takesplace. The reaction mixture is filte d While hot and then concentratedby dist. lemon under reduced pressure to about 20 cc. Upon cooling,l-amii1o-2trifiuoromethyl-e a-trifiuoromethylethylainino anthraqi loneprecipitates out and is recovered by filtration. It has the formula:

O NH H RF-ADHCH:

and colors cellulose acetate textile materials violet shades.

Example 6 10 grams of 1-c-hydroxyethoxyethylarhino-2-trifiuoromethyd--bromoanthraquinone, 4 grams of2,2,2-trifiuoroethylarnine, 3 grams of potassium acetate, 0.1 gram ofcopper sulfate and 166 cc. of n-butyl alcohol are refluxed togetheruntil no further color change toward the redblue takes place. Thereaction mixture is filtered While hot and the filtrate obtained isconcentrated to 415 cc. by a illation under r duced pres-- sure. Aftercooling, the reaction mixture is filtered andl43-hydroxyethoxyethylamino-2-trifluorcrnethyl 4 2,2,2trifiuorcethyla2n1no-anthraquinone having the formula:

is obtained. It colors cellulose acetate textile materials red-blueshades.

By the use of 4.5 grams of 3, ,S-trifiuoropropylarnine in place of2,2,2-trifluoroethylamine in the foregoing examplel-c-hydroxyethoxyethylamino-2-trifluoromethyl4-3,3,3trifluoropropylamino-anthraquinone which colors cellulose acetatetextile materials blue shades is obtained.

Example 7 it grams of l- -hydroxyethoxy-c-ethoxyethylamino 2trifluoromethywl-bron1oanthraquinone, grams or"2,2,2-trifiuoroethylamine,

cc. of n-butyl alcohol, 3 grams of potassium acetate and 0.1 gram ofcopper sulfate are heated together under reflux until no further colorchange toward the red-blue occurs. The reaction mixture is worked up asdescribed in Example 6 to obtain 1-e-hydroxyethoxy-p-ethoxyethylamino- 2-trifluoromethyl-4-2,2,2-trifluoroethylamino-anthraquinone which has theformula:

C Fa o I A) N-CHzOFs and which colors cellulose acetate textilematerials red-blue shades.

By the use of 4.5 grams of 3,3,3-trifluoropropylamine in place of2,2,2-trifluoroethylarnine in the foregoing example 1-8-hydroxyethoxy-p-ethox vethylamino-2-trifluoromethyl-4-3,3,3trifiuoropropylamino-anthraquinone which colors cellulose acetatetextile materials blue shades is obtained.

Example 8 10 grams of 1 amino 2 triiluoromethyl 4- bromoanthraquinone,4.3 grams of 2,2-difiuoropropylamine, 3 grams of potassium acetate, 0.1gram of copper sulfate and 100 cc. of n-butyl alcohol are heated underreflux. until no further color change takes place. The reaction mixtureis filtered while hot and the filtrate is conoentrated by distillationunder reduced pressure to about 40-45 cc. Upon cooling,1-amino-2-trifluoromethyl 4 2,2 difluoropropylamino anthraquinoneprecipitates out and is recovered by filtration. It colors cellu oseacetate textile materials violet shades from an aqueous suspension.

Example 9 10 grams of l amino 2 trifiuoromethyl 4 bromoanthraquinone, 4grams of 3,3-difluoropropylamine, 3 grams of potassium acetate, 0.1 gramof copper sulfate and 190 cc. of n-butyl alcohol are reacted togetherand worked up in the manner described in Example 8. l-amino-2-trifiuoromethyl 4 3,3 difluoropropylaminoanthraquinone is obtained. Itcolors cellulose acetate textile materials violet shades from an aqueoussuspension.

Example 10 10 grams of 1 amino 2 trifluoromethyl 4- bromoanthraquinone,grams of 3,3,3-trifluoropropylamine, 3 grams of potassium acetate, 0.1gram of copper sulfate and 100 cc. of n-butyl alcohol are reactedtogether and worked up as described in Example 6.l-amino-2-trifluoromethyl 4 3,3,3 trifluoropropylamino anthraquinone isobtained. It colors cellulose acetate textile materials red-blue shades.

Example 11 grams of l amino 2 trifluoromethyl 4 bromoanthraquinone, 5grams of 1,1-dif1uoro-2- aminopropane, 3 grams of potassium acetate, 0.1gram of copper sulfate and 100 cc. of n-butyl alcohol reacted togetherand the reaction mixture is worked up as described in Example 6. 1-amino 2 trifluoromethyl 4 a difluoromethylethylamino-anthraquinone isobtained. It has the formula:

0 NEz I] l C CFs o our;

II I o N-CHCH:

and colors cellulose acetate textile materials violet shades.

Example 12 10 grams of 1 p hydroxyethylamino 2 trifluoromethyl 4bromoanthraquinone, 3 .7 grams of 2,2-difluoroethylamine, 3 grams ofpotassium acetate, 0.1 gram of copper sulfate and cc. of n-amyl alcoholare reacted together and the reaction mixture is worked up as describedin Example 13 10 grams of l-'yhydroxypropylamino-2l-trifluoromethyl 4bromoanthraquinone, 4.7 grams of 2,2,2 trifluoroethylamine, 3 grams ofpotassium acetate, 0.1 gram of copper sulfate and 100 cc. of n-butylalcohol are heated together under reflux until no further change towardthe red-blue occurs. The reaction mixture is worked up as described inExample 6 to obtain 1-yhydroxypropylamino 2 trifluoromethyl 4 2,2,2trifluoroethylamino anthraquinone which colors cellulose acetate textilematerials red-blue shades.

By the use of 4.8 grams of 3,3,3-trifluoropropylamine in place of2,2,2-trifluoroethylamine in the foregoing example l-'-hydroxypropyfamino-2- trifiuoromethyl 4 3,3,3trifluoropropillaminoanthraquinone which colors cellulose acetatetextile materials blue shades is obtained.

Example 14 difluoroethylamino-anthraquinone which colors celluloseacetate textile materials red-blue shades.

By the use of 3.9 grams of 3,3-clifluoropropylamine in place of2,2-difluoroethylamine in the foregoing example l---hydroxypropylamino2- trifluoromethyl 4 3,3difluorcpropylaminoanthraquinone which colors cellulose acetate textilematerials blue shades is obtained.

Example 15 10 grams of1-{3-hydroxypropylamino-Z-trifluoromethyl-4-bromoanthraquinone, 4.7grams of 2,2,Z-triiiuoroethylamine, 100 cc. of n-butyl alcohol, 3 gramsof potassium acetate and 0.1 gram of copper sulfate are heated togetherunder Example 16 10 grams of 1-p-hydroxypropylamino-Z-trifluoromethyl 4bromoanthraquinone, 3 grams of potassium acetate, 0.1 gram of coppersulfate, 100 cc. of n-butyl alcohol and 3.8 grams of 2,2-difluoroethylamine are heated under reflux until no further color changetakes place. The reaction mixture is worked up as described in Example 6to obtain1-fi-hydroxypropylamino-2-trifiuorom-ethyl-4-2,2-difiuoroethylaminoanthraquinone which colors cellulose acetate textile materials red-blueshades.

By the use of 3.9 grams of 3,3-difluoropropylamine in place of2,2-difluoroethylamine in the foregoing example 1-B-hydroxypropylamino 2trifluoromethyl-4- .3 dirluoropropylamino anthraquinone which colorscellulose acetate textile materials blue shades is obtained.

Example 17 10 grams of l-,8,--dihydroxypropylamino-2-trifiuoromethyl-4bromoanthraquinone, 3 grams ofpotassium acetate, 0.1 gram of copper sulfate, 100 cc. of n-butylalcohol and 4.6 grams of 2, ,2- triiluoroethylamine are heated togetherunder reflux until no further color change toward the red-blue occurs.The reaction mixture is worked up as described in Example 6 to obtainl-f3,'ydl hydroxypropylamino 2 trifluoromethyl-4-2,2,2-

trifiuoroethylamino-anthraquinone which colors J cellulose acetatered-blue shades.

By the use of 4.0 grams of 2,2-difluoropropylamine in place of2,2,2-trifluoroethylamine in the foregoing example l6,v-dihydrOXypropylaminO 2-trifluoromethyl 4 2,2,difluoropropylaminoanthraquinone which colors cellulose acetate textilematerials blue shades is obtained.

sample 18 grams oflfl,'y-dihydroxypropylamino-2-trifiuoromethyl-4-bromoanthraquinone, 3grams of potassium acetate, 0.1 gram of copper sulfate, l cc. of n-butylalcohol and 3.7 grams of 2,2- difluoroethylamine are heated togetherunder reflux until no further color change toward the redblue occurs.The reaction mixture is worked up described in Example to obtainl-Bgy-dihydroxypropylamino 2 trifiuoromethyl-4-2,2-diflucroethylaminoanthraquinone which colors cellulose acetate textile materials red-blueshades.

By the use of 3.8 grams of 3 3-difluoropropylme in place ofZ-difluoroethylamine in the ing example l-c,ydihydroxyproplyaminofiucromethyl 4 3,3 difluoropropylaminoanthraquinonewhich color cellulose acetate textile materials blue shades is obtained.

Similarly, by the use of 9.5 grams of l-methylamino 2 trifiuoromethyl-.4 bromoanthraquinone in place of lum-dihydroxypropylamino-2-trifiuoromethyl 4. bromoanthraquinone in the foregoing examplel-methylamino 2 trifiuoromethyl-4-2,2-difluoroethylamino anthraquinoneis obtained. It colors cellulose acetate textile materials red-blueshades.

Example 19 10 grams of 1-ethylamino-2-trifluoromethyl-4-bromoanthraquinone, 3 grams of potassium acetate, 0.1 gram of coppersulfate, cc. of n-butyl alcohol and 4.8 grams of2,2,2-triiluoroethylainine are heated together under reflux until nofurther color change toward the red-blue occurs. The reaction mixture isworked up as described in Example 6 to obtain 1 ethylaminc 2trifiuoromethyl 4 2,2,2-trifiuoroethylamino-anthraquinone which colorscellulose acetate textile materials red-blue shades.

By the use of 4.9 grams of 1,1,1-triiluoroethyl- 2-aminopropane in placeof 2 2,2-trifluoroethylamine in the foregoing example lethylarcino2trifiuoromethyl 4 a trifluoromethylethylamino-anthraquinone is obtained.It colors c-elluolose acetate textile materials blue shades.

Example 20 10 grams of l-ethylamino-2-trifiuoromethyl-4-bromoanthraquinone, 3 grams of potassium acetate, 0.1 gram of coppersulfate, 100 cc. of n-butyl alcohol and 4 grams of2,2-difluoroethylan1ine are heated together under reflux until nofurther color change toward the red-blue occurs. The reaction mixture isworked up as described in Example 6 to obtain l-ethylamino 2trifiuoromethyl 4 2,2 difiuoroethylamino-anthraquinone which colorscellulose acetate textile materials red-blue shades.

Example 21 10 grams of l n propylamino 2trifiuoromethyl-4-bromo--anthraquinone, 3 grams of potassium acetate,0.1 ram of copper sulfate, 100 cc. of n-butyl alcohol and 4.7 grams of2,2,2-trifiuoroethylamine are heated together under reflux until nofurther color change toward the redblue occurs. The reaction mixture isworked as described in Example 5 to obtain l-n-propyh amino 2trifluoromethyl-4-2,2,2-trifluoroethylamino-anthraquinone which colorscellulose acetate textile materials red-blue shades.

By the use of 10 grams of l-isopropylatrifluoromethyl-4-bromo-anthraquinone ofl-n-propy1amino-2-trifiuoromethyl4 anthraquinone in the foregoingexample 1- V pylamino-2-trifluoromethyl 4 2,2,2trifiuorcethylainino-anthraquinone is obtained. It colors celluloseacetate textile materials blue shades.

mine 2 Example 22 10. grams ofl-n-propylamino-2-trifiuoromethyl-4-bromoanthraquinone, 3 grams ofpotassium acetate, 0.1 gram of copper sulfate, 100 cc. of nbutyl alcoholand 3.9 grams of 2,2-difluoroethylamine are heated together under r fluxuntil no further color change toward the red-blue occurs.

9 cellulose acetate textile materials red-blue shades is obtained.

Example 23 10 grams of 1-n-butylamino-2-trifluoromethy1-4-bromoanthraquinone, 3 grams of potassium acetate, 0.1 gram of coppersulfate, 100 cc. of n-butyl alcohol and 4.6 grams of2,2,2-trifluoroethylamine are heated together under reflux until nofurther color change toward the red-blue occurs. The reaction mixture isworked up as described in Example 5 to obtain l-n-butylamino- 2trifluoromethyl 4 2,2,2 trifluoroethylamino-anthraquinone which colorscellulose acetate textile materials red-blue shades.

By the use of 4.7 grams of l,l,l-trifluoro-2- aminopropane in place of2,2,2-trifluoroethylamine in the foregoing example l-n-butylamino- 2trifluoromethyl 4-a trifluoromethylethylamino-anthraquinone is obtained.It colors cellulose acetate textile materials red-blue shades.

Example 24 grams of 1n-butylamino2-trifluoromethyl-4-bromoanthraquin-one, 3.8 grams of 2,2-difluoroethylamine, 3 grams ofpotassium acetate, 0.1 gram of cupric acetate and 100 cc. of n-amylalcohol are refluxed together until no further color change toward thered-blue takes places. The reaction mixture is worked up in accordancewith the general procedure described in Example 6 to obtainl-n-butylamino-2-trifluorometh yl-4 2,2 difluoroethylamino anthraquinonewhich colors cellulose acetate textile materials red-blue shades.

By the use of 4 grams of 1,1-difluoro-2-aminopropane in place of2,2-difluoroethy1amine in the foregoing example1n-butylamino2-trifluoromethyl 4 a difiuoromethylethlyaminoanthraquinone which colors cellulose acetate textile materials red-blueshades is obtained.

Example 25 10 grams of 1-,8hydroxyethoxyethylamino-Ztrifluoromethyl-4-bromoanthraquinone, 4 grams of 2,2-difluoroethylamine,3 grams of potassium i acetate, 0.1 gram of cupric bromide and 100 cc.of n-butyl alcohol are refluxed togethe until no further color changetakes place. The reaction mixture is worked up in accordance with thegeneral procedure described in Example 6 to obtain1fl-hydroxyethoxyethylamino-2-trifiuoromethyl 4 2,2 difluoroethylaminoanthraquinone which colors cellulose acetate textile materials red-blueshades.

By the use of 4.3 grams of 3,3-difluoropropylamine in place of2,2-difluoroethylamine in the foregoing example 1 Bhydroxyethoxyethylamino 2 trifluoromethyl 4-3.3difluoropropylamino-anthraquinone which colors cellulose acetate textilematerials blue shades is obtained.

Example 26 10 grams of l-8-hydroxyethoxy-B-ethoxyethylamino-2-trifluoromethyl4-bromoanthraquinone,3.6 grams of 2,2difluoroethylamine, 100 cc. of pyridine, 3 grams ofpotassium acetate and 1 gram of copper sulfate are heated together underreflux until no further color change occurs. The reaction mixture isworked up in accordance with the general procedure described in Example6 to obtain 1-B-hydroxyethoxy-e-ethoxyethylamino- 2 trifluoromethyl 42,2difluoroethylaminoanthraquinone which colors cellulose acetate textilematerials red-blue shades.

By the use of 3.8 grams of 3,3-difluoropropylamine and 4 grams of3,3-difluorobutylamine, respectively in place of 2,2-difluoroethylaminein the foregoing example '1-fl-hydroxyethoxy-B-ethoxyethylamino 2trifiuoromethyl 4 3,3 difluoropropylamino-anthraquinone andl-fl-hydroxyethoxy ,8 ethoxyethylamino 2 trifluoromethyl 4 3,3difluorobutylainino anthraquinone, respectively, are obtained. Each ofthese compounds colors cellulose acetate textile materials blue shades.

cc. of n-butyl alcohol may be used in the foregoing example in place ofpyridine. Similarly, 0.1 gram of cupric acetate, oupric chloride orcupric iodide can be used as a catalyst in place of copper sulfate.

Example 2? 10 grams of 1-methylamino-2-trifluoromethyl-4-bromo-anthraquinone, 3 grams of potassium acetate, 0.1 gram of coppersulfate, 100 cc. of n-butyl alcohol and 4.5 grams of3,3-difluorobutylamine are refluxed together until no further colorchange takes place. The reaction mixture is worked up in accordance withthe general procedure described in Example 6 to obtainl-methylamino-2-trifluoromethyl-4-3,3-difluorobutylamino-anthraquinonewhich colors cellulose acetate textile materials blue shades.

By the use of 4.2 grams of 1,1-difluoro-2- aminopropane in place of3,3-difiuorobutylamine in the foregoing example1-methylamino-2-trifluorcmethyl-4adifluoromethylethylamino anthraquinonewhich colors cellulose acetate redblue shades is obtained.

Example 28 19 grams of l ethylamino-2-trifluoromethyl-4-bromoanthraquinone, 3 grams of potassium acetate, 0.1 gram of coppersulfate, 100 cc. of nbutyl alcohol and 4.1 grams of3,3-difluoropropylamine are heated together under reflux until nofurther color change takes place. The reaction mixture is worked up inaccordance with the I general procedure described in Example 6 to obtainl ethylamino 2 trifluoromethyl-4-3,3-difluoropropylamino-anthraquinonewhich colors cellulose acetate textile materials blue shades.

By the use of 4.4 grams of 3,3-difluorobutylamine in place of2,2-difluoroethylamine in the foregoing example 1 ethylamino 2trifiuoromethyl-4-3,3-.difluorobutylamino--anthraquinone which colorscellulose acetate textile materials blue shades is obtained.

Example 29 10 grams oflc-hydroxyethylamino2trifiuoromethyl-4-bromoanthraquinone, 3 grams ofpotassium acetate, 0.1 gram of copper sulfate, 100 cc. of n-butylalcohol and 4 grams of 2,2-difluoropropylamine are heated together underreflux until no further color change occurs. The reaction mixture isworked up in accordance with the general procedure described in Example2 to obtain l fi-hydroxyethylamino-Z-trifluoromethyl 4 2,2difluoropropylamino-anthraquinone which colors cellulose acetate textilematerials red-blue shades.

By the use of 4.0 grams of 3,3-difluoropropylamine and 4.2 grams of3,3-difluorobutylamine, respectively, in the foregoing examplel-e-hydroxyethylamino-2-trifluoromethyl-4-3,3-difluoropropylamino-anthraquinoneand l-p-hydroxyethylamino-2-trifiuoromethyl-43,3difluorobutylamino-anthraquinone, respectively, are obtained. Each ofthese compounds colors cellulose acetate textile materials blue shades.

Example 30 grams of1-c-hydroxyethylamino-2-trifluoromethyl-4-bromoanthraquinone, 3 grams ofpotassium acetate, 6.1 gram of copper sulfate, 100 cc. of n-butylalcohol and 4.3 grams of 3,3.3--tri fluoropropylamine are heatedtogether under reflux until no further color change occurs. The reactionmixture is worked up in accordance with the general procedure describedin mple 6 to obtain 1 3-b.ydroxyethylamino-2-tr fluoromethyl 4 3,3,3triiiuoropropylamino-anthraquinone which colors cellulose acetatetextile materials blue shades.

By the use of 4.3 grams of l,l,l-trifluoro-2- aminoprop-ane in place of3,3,3-trifiuoropropylamine in the foregoing examplel-B-hydroxtethylamino-Z-trifluoromethyl-4-a-trifiuorometnylethylamino-anthraquinonewhich colors cellulose acetate textile materials blue shades isobtained.

Example 31 10 grams of l-isopropylarnino-2trifiuoromethyli-bromo-anthraquinone, 3 grams of potassium acetate, 0.1 gram of coppersulfate, lilo cc. ofn-butyl alcohol and 4.3 grams of3,3,3-trifiuoroprcpylamine are heatedv together under reflux until nofurther color change occurs. The reac tion mixture is Worked up asdescribed in Example 6 to obtain l.isopropylamino2tr' iuoro1nethyl-4-3,3,3-trifiuoropropylamino anthi aquinone which colorscellulose acetate textile materials blue shades.

By the use of 4.1 grams of 3,3-dinucropropylamine and 4.4 grams of3,3-difiuorobutylamine, respectively, in place of3,3,3-trifluoropropylamine in the foregoing example l-isopropylamino 2trifluoromethyl-4-3,3-difluoro1 pyl amino-anthraquinone andl-isopropylamino-2 trifiuoromethyl 4 3,3 difiuorobutylamino-an--thraquinone, respectively, are obtained. Each of these compounds colorscellulose acetate textile materials blue shades.

Example 32 methyl 4-3,3-difiuorobutylamino-a1 which colors celluloseacetate textile materials blue shades is obtained.

Example 33 10 grams of 1-p-hydroxypropylamino-2-trfluoromethyl-4-bromoanthraquinone, 3 grams potassium acetate, 0.1 gramof copper sulfate, 1 cc. of n-butyl alcohol and 4 grams of33,3trifiuorcethylamine are heated togethe under flux until no furthercolor change occurs. The reaction mixture is Worked up in accordancewith the general procedure described 5 to obtain1-p-hydroxypropylamino-2-triiluoror 2 methyl 4 3,3,3trifluoropropylamino an thraquinone which colors cellulose acetatetextile materials blue shades.

By the use of 4 grams of 3,3-difiuorcbutylamine in place of8,3,S-trifiuoropropylamine in the foregoing examplel-,8-hydroxypropylamino- 2 triiiuoromethyl 4 3,3difluorobutylaminoanthraquinone which colors cellulose acetate textilematerials blue shades is obtained.

Example 34 10 grams ofl-whydroxypropylamino-2-trifluorornethyl-4-bromoanthraquinone, 3 gramsof potassium acetate, 0.1 gram of copper sulfate, cc. of n-butyl alcoholand 4 grams of 3,3-difiuorobutylamine are heated together under refluxuntil no further color change occurs. The reaction mixture is Worked upin accordance with the procedure described in Example 5 to obtain1whydroxypropylamino 2 trifluoromethyl 4 3,3difiuorobutylamino-anthraquinone which colors cellulose acetate textilematerials blue shades.

By the use of 4 grams of 1,1,l-trifiuoro-2- aminopropane in place of 3,3diiiuorobutylamine in the foregoing example lhydroxypropylamino 2trifluoromethyl 4 a triiiuoromethylethylamino-anthraquinone which colorscellulose acetate textile materials red-blue shades obtained.

Example 35 10 grams of 1-B,'y-dihydroxypropylamino-2- trirluoromethyl 4brcmoanthraquinone, 4.2 grams of 3,3,3-trifiuoropropylaniine, 100 cc. ofn butyl alcohol, 3 grams of potassium acetate and 0.1 gram of cupricacetate are heated together under reflux until no further color changeoccurs. The reaction mixture is filtered While hot and then concentratedby distillation under reduced pressure to about 40 cc. Upon cooling, 1[3,7 dihydroxypropylamino 2 trifluoromethyl 4 3,3,3trifluoropropyiarnino anthraquinone precipitates out and is recovered byfiltration. It colors cellulose acetate textile materials blue shades.

By the use of 4.1 grams of 3,3-difluorobutylamine in place of3,3,3-trifiuoropropylamine in the foregoing example 1p*,-dihydroxypropyl amino 2 trifluoromethyl 4 3,3diflucrobutylaniino-anthraquinone which colors cellulose acetate textilematerials blue shades is obtained.

Example 36 10 grams of1-methylamino-2-trifluoromethyla-bromoanthraquinone, 4.2 grams of2,2-difluoropropylarnine, 109 cc. of n-butyl alcohol, 3 grams ofpotassium acetate and 0.1 gram of cupric acetate are heated togetherunder reflux until no further color change occurs. reaction mixture isfiltered while hot and then concentrated by distillation under reducedpressure to about 4i) cc. Upon cooling 1-rnethylarnino-2-trifiuoromethyl 4 2,2 difiuoropropylaminoanthraquinone precipitates outand is recovered by filtration. It colors cellulose acetate textilematerials blue shades.

By the use of 4.2 grams or" 3,3-difiuoroprop l amine in place of2,2-difiuoropropy1amine in the foregoing example1-methylamino2-trifluoromethyl 4 ,3 difiuoropropylamino anthraquinonewhich colors cellulose acetate textile materials blue shades isobtained.

13 Example 37 10 grams ofl-methylamino-2-trifluoromethyll-bromoanthraquinone, 4.5 grams of3,3,3-trifluoropropylamine, 100 cc. of n-butyl alcohol, 3 grams ofpotassium acetate and 0.1 gram of copper sulfate are heated togetherunder reflux until no further color change occurs. The reaction mixtureis worked up in accordance the procedure described in Example 36 toobtain 1 methylamino 2 trifluoromethyl 4 3,3,3-trifluoropropylamino-anthraquinone which colors cellulose acetatetextile materials blue shades.

By the use of 4.5 grams of 1,1,1-trifluoro-2- aminopropane in place of3,3,3-trifluoropropylamine in the foregoing example l-inethylamino- 2trifiuoromethyl c c: trifluoromethylethylamino-anthraquinone whichcolors cellulose acetate textile materials blue shades is obtained.

Example 38 1c grams of1-n-buty1arnino-2-trifiuoromethyl--4-bromoanthraquinone, 5 grams of3,3-difluorobutylamine, 100 cc. of n-butyl alcohol, 3 grams of potassiumacetate and 0.1 gram of copper sulfate are heated together under refluxuntil no further color change occurs. The reaction mixture is Worked upin accordance with the procedure described in Example 36 to obtainl-n-butylamino 2 trifluoromethyl l 2,3 difiuorobutylamino-anthraquinonewhich colors cellulose acetate textile materials blue shades.

By the use of 5 grams of 3,3,3-trifluoropropylamine in place of3,3-difiuorobutylan1ine in the foregoing example1-n-butylamino-2-tri1luoro methyl 4 3,3,3 trifluoropropylaminoanthraquinone which colors cellulose acetate textile materials blueshades is obtained.

Example 39 grams of l- 3, -dihydroxypropylamino-2-trifluoromethyl-4-brom0anthraquinone,4.2 grams of1,Ll-trifluoro-Z-aminopropane, 100 cc. of nbutyl alcohol, 3 grams ofpotassium acetate and 0.1 gram of copper sulfate are heated togetherunder reflux until no further color change occurs. The reaction mixtureis filtered while hot and then concentrated by distillation underreduced pressure to about 40 cc. Upon cooling1-,3,'y-dihydroxypropylamino 2lJIiflUOI'OIIlBth5Il-4-a-tlifluoromethylethylamino anthraquinone whichcolors cellulose acetate textile materials red-blue shades is obtained.

By the use of 3.9 grams of 1,1-difiuoro 2-aminopropane in place of1,1,1-trifiuoro-2-aminopropane in the foregoing example1-B,y-dihydroxypropylamino-Z-trifluoromethy1 4 a difluoromehylethylamino-anthraquinone which colors cellulose acetate textile materials red-blueshades is obtained.

Many but not all of the limited number of compounds of our inventionhave been specifically disclosed in the foregoing examples. However, itis to be clearly understood that any of the members represented by R canbe present in the compound with an of the members represented by R1.Thus, compounds of our invention not specifically disclosed are preparedin accordance with the general disclosure given herein supplemented bythe numerous examples illustrating the manner in which the compounds ofour invention are prepared.

The anthraquinone dye compounds of our invention may be advantageouslydirectly applied to the material undergoing coloration in the form 14 ofan aqueous suspension which can be prepared by grinding the dye to apaste in the presence of a sulfonated oil, soap, sodium ligninsulfonate, or other suitable dispersing agent and dispersing theresulting paste in water.

Direct dyeing operations can, with advantage, be conducted attemperatures of about 65 C. C. but any suitable temperature can be used.Thus, the textile material such as cellulose acetate, for example, to bedyed or colored is ordinarily added to the dye bath at a temperaturelower than that at which the main portion of the dyeing is to beeffected. A temperature approximating 45 C.-55 C., for example,following which the temperature is raised to that selected for carryingout the dyeing operation. The temperature at which the dyeing isconducted may, of course, be varied somewhat depending upon theparticular material undergoing coloration. As is understood by thoseskilled in the dyeing art the intensity of dyeing can be varied byvarying the proportion of dye to material undergoing coloration. Theamount of dye used can be, for example, to 3% (by weight) of that of thetextile material, although lesser or greater amounts of dye can be used.

The term copper sulfate as used in the foregoing examples is intended tomean CUSO l'5H20.

In order that the preparation of the anthraquinone compounds of ourinvention may be entirely clear, the preparation of various intermediatecompounds used in their manufacture is described hereinafter.

Compounds having the formula:

n N-R o 0 r3 (3 J H 0 Br I wherein R has the meaning previously assignedto it are prepared by brominating a compound having the formula:

0 wherein R has the meaning previously assigned to it.- The brominationis carried out in an inert diluent such as pyridine at a temperature ofabout C. using bromine as the brominating agent. Preferably an excess(5-10 per cent) of bromine is employed. The time required for thebromination is ordinarily 5 to 6 hours. The process will be illustratedWith reference to the preparation of1-methylamino-2-trifluoromethyl-a-b.romoanthraquinone.

Example A 25 parts of 1-methylamino-Z-trifluoromethylanthraquinone aredissolved in 1&9 parts of pyridine and brominated at 100 C. with bromine(5-10 per cent excess over the amount theoretically required) for 5 to 6hours. The reaction mixture is then cooled. The l-methylarnino-Z-trifluoromethyl 4 bromoanthraquinone formed in the reaction crystallizesout and is recovered by filtration. It can be used as obtained in purerform by recrystallization from pyridine,

In an exactly similar way by the use of an equivalent molecular weightof another compound of Formula II for1-methylamino-2-trifluoromethylanthraquinone in Example A, othercompounds of Formula I are readily prepared. Thus, by using anequivalent molecular weight of 1-amino-2-trifluoromethylanthraquinone,1-6- hydroxyethylarnino 2 trifiuoromethylanthrauinone, 1-p-hydvethoxyethylamino-2-trifiuoromethylanthraqu one, etc., respectively, inplace of 1-methylamino-2trilluoromethylantl aquinone ple A1-amino-2-trifluorcmethyl- -bro;.noa 'hraquinone, ll-dhydroxyethylaml-brcmoanthraquinone,l-fi-hydroxyethoxyethylamino'-4-bromoanthraquinone, etc., respectively,are obtained.

Compounds having the Formula I can also be prepared by brominating acompound having the Formula II in accordance with the general procedureillustrated hereinafter with reference to the preparation ofl-amino-2--trifiuoromethyle-bromoanthraquinone.

Easample B.-1-amino-Z-trifluoromethyl- 4 -bromocmthraquinonelamino-2--trifluorcrnethylane are dissolved in 250 grams of sulfuric gr.1.84) at about 50 C-60 C. The resulting solution is poured with goodStirring into 3.5 liters of water containing 5 grams of ferrous sulfate.To this mixture is then added with vigorous stirring 88 grams of bromineover a period of 4 hours at 55 C. 60 C. and the reaction mixture isstirred for about 5 hours after the addition of the bromine. By the useof a slight positive pressure the time needed for bromination can bereduced. 1-amino-2-trifiuor0- methyl-l-bro1noanthraquinone is recoveredby filtration as an orange red solid. It is washed well and dried. Theyield obtained is nearly quantitative.

As above stated, the general procedure described in Example can be usedto prepare other compounds having the Formula I. To illustrate, by theuse or" an equivalent molecular weight of another compound of Formula IIfor 1-amino-2- trifiuoromethylanthraquinone in Example B other compoundsof Formula I are readily prepared. Thus, by using an equivalentmolecular weight of 1-11-butylamino-2-trifluoromethylanthraquinone andl-/3-hydroxyethoxyethylamino-2-trifiuoromethylanthraquinone,respectively, in place of l-amino-Z--trifiuoromethylanthraquinone inExample B l-n-butylamino-2- ulay he-bremoanthraquinone and 1-13-hydroxyethoxyethylamino 2 trifluoromethyl 4t-bromoanthracguinone,respectively, are obtained.

Compounds having the Formula II are preby reacting1--chime-2-trifiuoromethylanthraquinone with a primary amine having theformula: H2NPt, wherein R has the meaning previously assigned to it. Thefollowing example illustrative of the manner in which compounds hav'Formula II are prepared.

Example C'.1-fl-hydroccyethylamino-2-trifluo- Tomethyianthraquinoneeholro 2 trifiuoromethylanof pyridine and parts romethylanthraquinonecrystallizes out and is recovered by filtration, washed well with waterand dried. It is a reddish-brown solid that colors cellulose acetatetextile materials red shades from an aqueous suspension. The yield isabout per cent.

By the use of an equivalent molecular weight of another amine of theformula: H2NR1, wherein R1 has the meaning previously assigned to itother compounds of the Formula II are readily obtained. Thus, by the useof methylamine and ethylamino, respectively, l-methylamino 2trifiuoromethylanthraquinone and 1 ethylamino 2 trifiuoromethylanthraquinone, respectively, are obtained. Ammonia is ordinarily used in the formof ammonium hydroxide. Thus, by the use of strong ammonium hydroxide inExample Bin place of ethanolamine 1-amino-2-trifiuoromethylanthraquinoneis obtained.

The preparation of l-chloro-2-trifiuoromethylanthraquinone is describedin Example 2 of German Patent 713,745. 1-amino2-trifiuoromethylanthraquinone is disclosed in U. S. Patent 2,061,186.Neither of these two patents, however, discloses anthraquinone compoundsof the character described and claimed by us.

Certain amines of the formula: H2NR1, wherein R1 has the meaningpreviously assigned to it are new compounds. The preparation of thesenew compounds is described hereinafter.

In general, the above-identified amine compounds are prepared byreacting concentrated aqueous ammonia with a fiuorinated alkyl halide(Cl, Br or I) compound corresponding to the amine compound to beprepared. 2,2,2,-trii'luoroethylamino and 3,3,3,-trifluoropropylamineare specifically disclosed in U. S. Patent 2,348,321. The example givenin this patent is illustrative of the manner in which the reactionbetween the fiuorinated alkyl halide and ammonia is carried out.Ordinarily, the fiuorinated alkyl halide employed is a fluorinatedaliryl chloride.

2,2-difluoroetl'iylamine is disclosed in Bull. sci. acad. roy. Belg,page 762 (1904). It can also be prepared by reacting CHFzCl-lzCl,CHFzCHzBr or CHF2CH2I (all known compounds) with aqueous ammonia.Similarly 3,3-difiuorobutyla1nine can be prepared by reacting the knowncompound CH3CF2CH2CH2C1 with aqueous ammonia. The reactions justreferred to can be carried out in accordance with the general proceduredescribed in U. Patent 2,348,321.

Preparation of 2,2-difluoropropyla7nine 48 grams of CH3CF2CH2BI', J. A.C. S. V01. 59, page 2434 (1937) are heated with 200 cc. of 28% aqueousammonia and 1 gram of a wetting agent such as Nacconol NR (sodium alkylnaphthalene sulfonate) in a shaking autoclave at C.-l50 C. for 24 hours.The reaction mixture is then carefully distilled through an enicientfractionating column, NHs gas coming off first. The amine fractiondistilling over from 60 C.85 C. is then collected and dried over solidNaOH and then finally redistilled from fresh solid NaOH.2,2-difluoropropylamine distills over at 75 C.77 C. and has a refractiveindex of N9 1.362. It is a water white liquid miscible with water andwith other ordinary organic solvents, and has a characteristic amineodor.

34.6 grams of CHsCFzCIHzCl can be substituted for the CI-IgCF'zCHzBr ofthe foregoing example.

Preparation of 3,3-difiuor-op1iopylamme 13c grams of1,1-difluoro-3-bromopropane,

11: CHF2CH2CH2BI, and 328 cc. of 28% aqueous ammonia were heated withshaking in an autoclave at 110 C.-120 C. for 24hours. The autoclave wasthen cooled and-"the cooled contents were removed and poured into 5 grammoles of cold hydrochloric acid, fiitered and evaporated to dryness on awater bath and under -30 mm. pressure. The aminesalts'formed were thensepad. flfom the ammonium chloride formed by extraction witli 3-200 cc.portions of absolute ethyl alcohol. The ethyl alcohol solution wasevaporated to dryness and treatedwith an aqueous solution of potassiumhydroxide; (150 grams :KZOH 'ahd' 150 be. water.) The. reactionrmixtureseparated into two layers and was extracted with ethyl eth e r anddried. On distillation of the ether extract, there was obtained: 1)3,3;difluoropropylamine which boils at,92 C. 9i.C at 1760:mmwand'whichhah a reiractivegindex of N 1.3650 and2)'bis=-3;3=difluoropropylamine which boils at or cact c. at 50 mm.and'which has a refractive index of N 1.3744. Both are colorlessliquids.

Calculated Found Analysis of 1:

W Ne t s m zooao who Preparation of 1,1,1-trifluoro-2-aminopr0pane1,1,1-triiiuoroacetone was heated in an auto clave at 90 C.-100 C. for 5hours with a water solution of hydroxylamine hydrochloride and sodiumacetate to form the oxime. The process is substantially the same as thatemployed by Swarts, Bull. sci. acad. roy. Bela, page 178 (1927) grams ofthe oxime reaction product obtained as just described was hydrogenatedin ethyl ether in an autoclave under 2000 pounds hydrogen pressure usingHaney nickel as a catalyst. Upon completion of the hydrogenationreaction the ether solution was filtered and the filtrate was acidifiedwith etheral hydrogen chloride to obtain 1,1,l-trifluoro 2-aminopropanein its hydrochloride form, which was recrystallized from its solution inethyl alcohol-ethyl ether.

Calculated for CsHvClFzN: C, 24.4; H, 4.7; N, 9.4. Found: C, 24.3; H,4.6; N, 9.3.

The free amine was obtained from the amine hydrochloride by treatingwith an aqueous 50% KOH solution and distilling off the amine. It boilsat 46 C.47 C. at 760 mm. and has a refractive index of N 1.3210.

1,1,l-trifiuoro-2-aminopropane can also be prepared by reactingCFsCHBI'CHs with concentrated aqueous ammonia in an autoclave.

Preparation of 1,1-difluoro-Z-aminopropane NH: (CHFzJHOHa) This compoundis prepared in accordance with the procedure described in connectionwith 1,1,1-

trifluoro 2-aminopropane. That is, difluor-oacetone, CHF2COCH3 isconverted to the oxime by treatment with a water" solution of hydroxyl-1.8 oxime is converted to 1,11-difiuoro-2-aminoproe pane in accordancewith the procedure usedpin the case of 1,1,1-trifluoro-2-aminopropane.

1,1 difluoro-2-aminopropane can also be pre pared by reactingCHFzCHBrCHswith concern trated aqueous ammonia in an autoclave.

Preparation of 3,3-difluorobutylamibe 32.1 grams of1-chloro-3,3-difluorobutane were placed in the glass linerof anautoclave together with 102 cc. (1.5 gram-molef'of aqueous ammonia. Thereactants were heated at 120 C.125 C. with shaking for 24 hours j Theautoclave was then cooled a'nd the contents neutralized by pouring-intoa small excess of iced dilute hydrochloric acid. The reaction mixtureresulting was then distilled andl concentrated? to dryness on a steambath under reduced pressure;

The dry residue of the amine hydrochloride and ammonium chloride wasextracted four times with hot absolute ethyl alcohol. This treatmentseparates the alcohol soluble amine hydrochloride from the insolubleammonium chloride. The alcohol extracts were concentrated to drynessyielding 25.4 grams (70%) of CHsCFzCI-IzCHzNI-Iz HCl which were furtherpurified bycrystallization from ethyl alcohol-ethyl ether. l

The free amine was obtained by heating the amine hydrochloride with anexcess of dimethyl aniline and distilling off the amine.

Preparation of 1,1 -dz'flworo-3-bmmopropame 98 grams of1,1,3-tribromopropane (CHBrzCHzCI-IzBr) were placed in a 200 cc. roundbottomed flask fitted with a still-head and a well-cooled receivingflask. 107 grams of dry mercuric fluoride-were added to the reactionflask which was then heated gently with a free flame until reactionbegan. The reaction was then allowed to proceed briskly but not toovigorously (by cooling or heating as required) until all the reactionproduct had distilled over at about C.- C. The crude product was thensteam-distilled, dried and fractionated by distillation under reducedpressure. The main product obtained was 1,1-difluoro-3-bromopropane(CHFzCI-IzCI-IzBr) having a boiling point of 92 C.94 C. A yield of35-40% of pure product was obtained. A small amount of cHzFCI-IzCHzBrwas present in the still residue.

We claim:

1. The anthraquinone compounds having the formula:

H O N-R g l -CFs I l-R1 H wherein R stands for a member selected fromthe group consisting of a hydrogen atom, an alkyl group having 1 to 4carbon atoms, a hydroxyalkyl group having 2 to 3 carbon atoms, a

group and, R1 stands for a member selected from the groupconsisting of a2,2-difiuoroethyl ardup, I

19 20 a 2,2-difluoropropy1 group, a, 3,3'difluoropropyl H group, a3,3-difiuorobutyl group, a 2,2,2-trifluoro- Q B ethyl group, a3,3,3-trifluoropropy1 group, an 0 a-trifiuoromethylethyl group and ana-difluoromethylethyl group. 8

2. The anthraquinone compound having the G formula. 1% N-CHzCF:

O NH: H g m JOSEPH B. DICKEY. 0F; EDMUND B. TOWNE.

REFERENCES CITED The following references are of record in the 15 fileof this patent: 3.. The anthraquinone compound. having the UNITED STATESPATENTS formula: Number Name Date 2,050,704 Koeberle et a1. Aug. 11,1936 5 NH; 20 2,061,186 Cole Nov. 17, 1936 0 2,085,736 Calcott et a1July 6, 1937 2,174,182 Schlichenmaier et aLSept. 26, 1939 2,211,943Wilder Aug. 20, 1940 \O/ 2,333,402 Wuertz et a1 NOV. 2, 1943 A N CH CHF2,451,478 Dickey et a1 Oct. 19, 1948 H OTHER REFERENCES 4. The an hrquin n mp vi the Gilman, Ed. Organic Chemistry, 2nd ed. 1943, formula:vol. I, pp. 956, 960, 963.

1. THE ANTHRAQUINONE COMPOUNDS HAVING THE FORMULA: